Process of desulfurizing petroleum distillates.



H. V. WALKER. PROCESS OF DESULPURIZING PETROLEUM DISTILLATES.

APPLICATION FILED iEB.6, 1909.

Patented Apr. 19,1910.

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PROCESS OF DESULFIIRIZING To all whom 'it may concern:

Be it known that I, HENRY V. WAIKER, a citizen of the United States, and resident of Brooklyn, in the county of Kings and State of New ork, have invented certain new Improvements in the Process of Desulfurizing Petroleum Distillates, of which the following is a specification.

This invention relates to a process of desulfurizing petroleum distillates for the pur-' pose of removing therefrom the sulfur compounds which impart to them an ofiensive odor by reason of which they are rendered unfit for many uses. This offensive odor is particularly characteristic of the oils of the Lima class and is due to the presence of sulfur in organic combination which cannot be removed by ordinary methods but which passes over into the from the still with the vapors of leum distillates. A

Many attempts have been made to remove the sulfur from these oils and the most sucown' to me depends on the use of oxidof copper. But this process isnot completely successful and has other disadvantages not necessary to state here.

I have discovered that the desulfurizati'on of these oils may be better and more readily accomplished by the use of anhydrous chlorid of copper and the best method known for carrying out this process is as follows: I take a suitable quantity of the ordinary crystallizedchlorid of copper and heat it until all of the .water, including the water of crystallization, is driven off, when it presents the appearance of a soft brown or red powder. The petroleum distillates may be subjected to the action of this an.- hydrous chlorid of copper by adding'a small quantity ofthe powderto the oil, agitating the mass of the oil to produce thorough contact, removing the oil and washing it with water and distilling off the petroleum distillates, if necessary. This process is appliof refining,

condenser the petrobeen already distilled and condensed. I carry out the process dist-illates are in the The vapors producedin any stage 0 the distillation process may be employed and a convenient and eflicient way anhydrous chlorid of copper is to pass them through an apparatus in the form .of a col- Specification of Letters Patent. Application filed February 6,

' offensive odors surface of an alkaline lead rnrnonnunr DISTILLA'IES.

Patented Apr. 19, 1910.

1909. Serial No. 476,357.

umn containing the chlorid of copper in the form 0 der on a number of shelves vapors must come in contact as they pass through the column. If it is found that the vapors passing out of this kind of an apparatus -while free from still contains a small amount CID of sulfur in the form of sulfureted hydrogen, it may be removed by passing such vapors through an alkaline lead solution.

This is the ordinary plumbate of soda solution made by dissolving oxid of lead in a solution of caustic soda. stood, of course, that the vapors described takes pla ture high enough to maintain them in the form of vapor and that after the reaction has taken place they are condensed and collected in a suitable vessel.

In the annexed drawing. is shown diagrammatically an apparatus in which the described process may be carried out.

1 is the still to contain the petroleum distillate -to be treated, said still being heated in any suitable manner as by the live steam coil 2. The still may be filled through the inlet 3 and emptied at the valve cont-rolled opening 4. A pipe 5 leads the vapors to the apparatus 6 containing perforated. shelves upon which is supported the anhydrous copper chlorid. The petroleum vapors, having passed through these perforated shelves and the copper chlorid, an fied, are delivered by pipe 8 down below the solution or its equivalent contained in vessel 9, whence the It will be undertreatment of the ce at a temperabeing thus purifinal vapors escape by pipe 10 leading to i a condenser not shown. A gage glass 11 is shown on the tank 9, also a valve cont-rolled outlet '12. This tank will also naturally be provided with filling inlet, not shown however in, the drawing;

This process yields a fluid entirely free from the offensive odor of the original and as colorless and limpid as water and one which will stand the tests usually applied to apparatus to convert it to an oxid and then treating it with hydrochloric acid to reconvert it lnto'chlorid .of copper which is dehydrated in the manner as above described,

gradually converted into sulfid' when it ma be used over again. The amount of ch orid of copper to be employed depends, of course, upon the amount of sulfur in the oil to be treated and in any .particular case the proportion should be determined b previous experiment and calculation. Vi en gas naphtha has been the material treated I have found that about two parts by weight of the anhydrous chlorid of copper to one hundred parts by weight of the gas naphtha is a suitable proportion.

Anhydrous copper chlorid dissolves in and seemingly forms a double compound with the sulfur bearing oil, which compound thereafter splits up into sulfid of copper, hydrochloric acid, and the sulfur-free oil. This is not true of copper sulfate which, whether anhydrous or not, is not taken up by the oil, forms no double compound, and is practically without efiect in removing organically combined sulfur.

The alkaline lead solution as used above is not for the purpose of desulfurizing the oil, as this is completely effected by the anhydrous copper chlorid treatment. On the contrary, its pur ose is to remove the small amount of sul 'ureted hydrogen roduced by the action of the liberated by rochloric acid upon the liberated copper sulfid. Similarly, the lead solution takes up said hydrochloric acid.

What I claim as new is:-

1. The process of desulfurlzing petroleum distillates which consists first, in dehydrating chlorid of copper to remove the water of crystallization, and second, passing the petroleum distillates in the form of vapor over the anhydrous chlorid of copper thus formed and condensing the vapors.

2. The process of desulfurizing petroleum distillates which consists first, 1n dehydrating chlorid of copper to remove the water of crystallization, second, passin the petroleum distillates in the form 0 vapor over the anhydrous chlorid of copper thus formed and through an alkaline lead solution, and third condensing the purified vapors.

3. The process of treating gas naphtha and similar hydrocarbon compounds for the removal of sulfur present in organic combination which consists in subjecting the same to the action of anhydrous chlorid of copper.

4. The process of treating gas naphtha and similar hydrocarbon compounds for the removal of sulfur present in organic combination which consists in subjecting the same to the action of anhydrous chlorid of copper, in the proportion of two parts by weight of the latter and one hundred parts by weight of the former.

5. The process of treating petroleum compounds containing sulfur which consists in passing the same in the form of vapor over anhydrous chlorid of copper and through an alkaline lead solution.

-6. As a step in the process of manufacturing petroleum distillates, the subjection of the same, or their vapors of distillation before condensation, to the action of anhydrous chlorid of co per.

Witness my ban this fourth day of February 1909, at New York, N. Y.

HENRY v. WALKER.

Witnesses:

WILLIAM R. BAIRD, STEPHEN S. Nnwron. 

